Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/064—Polymers containing more than one epoxy group per molecule
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
  • C08G18/168—Organic compounds
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/248—Catalysts containing metal compounds of tin inorganic compounds of tin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3237—Polyamines aromatic
  • C08G18/324—Polyamines aromatic containing only one aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/325—Polyamines containing secondary or tertiary amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
  • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/58—Epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/58—Epoxy resins
  • C08G18/588—Epoxy resins having silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/60—Polyamides or polyester-amides
  • C08G18/603—Polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
  • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
  • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5026—Amines cycloaliphatic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives

Definitions

• the present invention relates to a two- or multi-part composition that can be fixed by irradiation and cured at room temperature or optionally by heating.
• the composition comprises at least one at least bifunctional nitrogen-based curing agent for epoxy compounds, a hybrid compound having both radiation-curable groups and epoxy groups crosslinkable by polyaddition, and a photoinitiator.
• the invention relates to a method for the joining, coating, molding or casting of substrates using the two- or multi-part mass.
• two-part compositions offer the advantage that systems can be provided which are storage-stable at room temperature for long periods.
• the curing reaction does not start before the components are brought together and mixed. This proves to be useful, particularly in large-scale industrial applications.
• EP 0 245 559 B1 discloses two-part compositions on the basis of epoxides and amines, as the curing agent, which additionally contain another radiation-curable compound and a photoinitiator in the epoxy resin component.
• the curing agent such amines are selected that are less reactive to addition to the double bond of the (meth)acrylates.
• Primary amines in particular, after mixing of the components, are spent uncontrolledly by addition to the acrylate groups of the radiation-curable compound, and are no longer available for curing of the epoxy groups. At the same time, the proportion of radiation-curable groups is reduced. Due to this side reaction, the maximum initial strength that can be achieved by light fixation becomes dependent upon the time of irradiation after mixing of the components.
• Another disadvantage is the lack of freedom of formulation when selecting the curing agent. Even by selecting less reactive amines, undesired addition reactions cannot be completely excluded, leading to different properties between irradiated and non-irradiated areas in the cured composition.
• U.S. Pat. No. 5,057,348 A describes casting compositions based on two-part systems. Apart from various amine curing agents, they also contain acrylates of a higher functionality. In these compositions, reaction of the curing agents with the acrylate constituents is similarly uncontrolled as in the case of EP 0 245 559 B, also leading to properties in the cured composition that are inhomogeneous and difficult to reproduce, as the networks formed essentially depend on the chronological order of the process steps. This is particularly disadvantageous for casting compounds requiring a reliable tension compensation.
• WO 2018/011116 A1 discloses a method of generating a property gradient in a cured composition using light-fixable epoxy-amine compositions that additionally contain a radiation-curable acrylate compound and a photoinitiator.
• the different reaction speeds of the amines as compared to the acrylates and epoxy resins in conjunction with irradiation are specifically used to generate variable mechanical properties.
• precise shading of selected areas is required during irradiation to achieve various moduli of elasticity in the joint. Considering the increasing miniaturization of many parts in practice, this can often not be implemented with reasonable effort and expense.
• the described compositions cannot be formulated as two-part compositions in a storage-stable form.
• the light-fixable two-part compositions described in the state of the art have a limited freedom of formulation and/or differences in the mechanical properties between irradiated and non-irradiated zones that are difficult to control.
• compositions should have a broad formulation range with respect to the curing agents.
• compositions should have sufficient dimensional stability in the light-fixed state to offer a wide range of applications in which initial fixation of parts by irradiation with actinic radiation is advantageous prior to processing the parts in further processes.
• compositions according to the present invention are intended to be processable, without limitation, within a period of time reasonable for the respective application.
• the mechanical properties of the cured composition should differ as little as possible between irradiated and non-irradiated zones and be independent of the time of irradiation.
• composition according to the present invention are stated in the sub-claims, which can optionally be combined with each other.
• composition according to the present invention comprises the following components: (a) optionally an at least bifunctional epoxy-containing compound; (b) an at least bifunctional nitrogen-based curing agent suitable for epoxy curing; (c) a radiation-curable compound comprising at least one hybrid compound, wherein the hybrid compound has both one or more radiation-curable methacrylate groups and one or more epoxy groups; (d) a radical photoinitiator; (e) optionally an accelerator for epoxy curing, and (f) optionally further additives.
• the components of the two- or multi-part composition according to the present invention are preferably liquid at room temperature, and can be fixed by irradiation with actinic radiation after being mixed with each other. After mixing, the composition cures at room temperature within a few days or hours. Optionally, curing can be accelerated by heat.
• compositions according to the present invention are particularly suitable for the manufacture of optoelectronic structures and the production of electric motors.
• the invention further relates to a method for the joining, coating, molding or casting of substrates using the composition according to the present invention.
• the composition applied to a substrate can be transferred into a dimensionally stable state by irradiation, and the composite can be further processed in subsequent process steps.
• the irradiated composition can, for example, be eventually heat-cured in a furnace process.
• the two-part composition according to the present invention shows no substantial differences either in the irradiated or the non-irradiated areas regarding the mechanical properties, in particular with respect to the modulus of elasticity, the glass transition temperature and/or the elongation at break.
• the processing time and the mechanical properties of the composition can be set by selecting from a wide range of epoxy compounds and curing agents as well as by the optional addition of accelerators and/or additives.
• two- or multi-part or “two- or multi-part composition” means that the reactive compoonents of the composition are physically separated from each other.
• the compositions according to the present invention are formulated as two-part compositions.
• the separated components are also referred to as resin component (A) and curing agent component (B).
• the resin component (A) and the curing agent component (B) can be composed of several (single) components which are compatible with each other. In the following, when referring to two-part compositions, these also comprise multi-part compositions.
• compositions For easy use of the compositions, the use of double-chamber cartridges (e.g. Mixpac series by Sulzer) is useful. Preferred volume mixing ratios of components (A)/(B) are in a range of 2:1 to 1:1. Static mixing tubes can be used for mixing and dosing.
• liquid means that the loss modulus G′′ determined by measuring the viscosity is larger than the storage modulus G′ of the respective component at 23° C.
• At least bifunctional means that, per molecule, two or more units of each functional group named are contained. No distinction is made between primary, secondary or tertiary functional groups.
• the mass (m) containing one mole of active hydrogen functionalities directly linked to a nitrogen atom is referred to as the active hydrogen equivalent weight (AHEW).
• AHEW active hydrogen equivalent weight
• AHEW [g/mol] m [g]/ n act-H [mol].
• the mass (m) containing one mole of epoxy functionalities is referred to as the epoxy equivalent weight (EEW).
• EEW [g/mol] m [g]/ n epoxy [mol].
• SEW radiation-curable equivalent weight
• the epoxy compound (a) is not further restricted in terms of its chemical structure and preferably comprises aromatic or aliphatic compounds having at least two epoxy groups in the molecule, such as glycidyl esters, glycidyl ethers, glycidyl amines, and mixtures thereof.
• component (a) can also contain monofunctional epoxy compounds as reactive diluents.
• aromatic glycidyl ethers are used in the compositions according to the present invention. They can be obtained from the reaction of epichlorohydrin with aromatic alcohols and phenols. Examples of such aromatic epoxy compounds and their respective trade names are bisphenol A epoxy resins (D.E.R. 331, Epikote Resin 828), bisphenol F epoxy resins (Epikote Resin 862, Epikote Resin 863, YDF-170), mixtures of bisphenol A and F diglycidyl ethers (D.E.R. 351, Epikote Resin 166, YDF-161), phenol-novolac epoxy resins (D.E.N. 424, D.E.N. 437, D.E.N. 440, YDPN-631) and cresol-novolac epoxy resins (DIC Corporation Epiclon N-670, YDCN-500-5P).
• bisphenol A epoxy resins D.E.R. 331, Epikote Resin 828
• bisphenol F epoxy resins
• glycidyl ethers based on aromatic alcohols such as 1,6-dihydroxynaphthalene (Araldite MY 0816), tris(hydroxyphenyl)methane (Tactix 742), various bisphenols, hydroxy-substituted biphenylenes (e.g. jER YX4000H) or monofunctional glycidyl ethers, e.g. on the basis of p-tert-butylphenol (D.E.R. 727), cardanol (Cardolite NC-513) or nonylphenol (Erisys GE-12), can be used.
• aromatic alcohols such as 1,6-dihydroxynaphthalene (Araldite MY 0816), tris(hydroxyphenyl)methane (Tactix 742), various bisphenols, hydroxy-substituted biphenylenes (e.g. jER YX4000H) or monofunctional glycidyl ethers, e
• diglycidyl ethers on the basis of aliphatic alcohols such as butanediol (Araldite DY-D), hexanediol (Araldite DY-H), cyclohexanedimethanol (Araldite DY-C), polymeric diols (e.g. polyoxypropylene glycol, Araldite DY-F), dicylopentadiene dimethanol (Adeka EP 4088S) or amines and aminophenols such as TGAP (triglycidyl ether of aminophenol; Araldite MY 0610) or TGMDA (tetraglycidyl ether of methylenedianiline, Araldite MY 721) can be used.
• TGAP triglycidyl ether of aminophenol
• Araldite MY 0610 triglycidyl ether of aminophenol
• TGMDA tetraglycidyl ether of methylenedianiline
• Hydrogenated bisphenol A and bisphenol F epoxy resins e.g. Eponex Resin 1510 are preferred.
• Isocyanurates substituted with epoxy-containing groups and other heterocyclic compounds can also be used as component (a) in the compositions according to the present invention.
• examples are triglycidyl isocyanurate and monoallyldiglycidyl isocyanurate.
• mono- and polyfunctional epoxy resins of all resin groups named containing, apart from the epoxy functionalities, additional functional groups can be used.
• OH-functional oligomeric aromatic epoxy compounds e.g. Dow D.E.R. 671 or Kukdo KD-9004.
• Addition products of the epoxy compounds listed with H-acidic compounds such as carboxylic acids, alcohols and/or thiols can be used as well.
• Particularly preferred examples are reactive liquid rubbers, e.g. addition products of epoxy compounds with CTBN rubber (e.g. Albipox 2000) or dimer fatty acids (e.g. B-Tough A3).
• a combination of several epoxy-containing compounds at least one of which is bifunctional or of a higher functionality is also in the sense of the invention.
• component (a) is preferably present in a proportion of 0 to 80 wt-%, based on the total weight of components (a) to (e). Particularly preferably, the proportion of component (a) is from 10 to 65 weight percent.
• Monofunctional epoxy compounds can be contained in component (a) in a proportion of up to 20%, particularly preferably up to 10%, based on the total weight of component (a).
• the at least bifunctional nitrogen-based curing agent (b) for epoxy curing is preferably selected from the group of primary and secondary amines, and comprises compounds with at least two amino groups per molecule suitable for epoxy curing.
• Component (b) is not further restricted in terms of its chemical structure, and preferably comprises aromatic, aliphatic, cycloaliphatic amines, polyamines, (poly)ether amines, amine-modified rubbers, N-containing heterocyclene and amine adducts such as polyamides, polyamidoamines and Mannich bases, and combinations thereof.
• the at least bifunctional amine is selected from the group consisting of aliphatic or cycloaliphatic amines, polyether amines, polyamides, Mannich bases or their reaction products with epoxy resins, and combinations thereof.
• EDA ethylenediamine
• DETA diethylenetriamine
• TETA triethylenetetraamine
• N-AEP aminoethylpiperazine
• BAPP N,N′-bis(3-aminopropyl)piperazine
• cycloaliphatic amines are, for example, isophorone diamine (Evonik, Versamid IPD), octahydro-4,7-methanoindene-1(2),5(6)-dimethane amines (Oxea, TCD-diamine), piperazine (DowDuPont) or Jeffamine RFD-270 from Huntsman containing both cycloaliphatic and polyether building blocks.
• (Poly)ether amines can be obtained from Huntsman (examples: Jeffamine T-404, T-3000, THF-100, DER-148, ED-600, D-230, D2000), Hexion (EPIKURE Curing Agent 3230, 3233) or BASF (Baxxodur EC 130, EC 302, EC 311).
• Amine adducts are reaction products of amines and further constituents and comprise, for example, polyamides (Versamid 140), polyamidoamides (Aradur 955) or Mannich bases (Epikure Curing Agent 105 or 110, Cardolite NC-557).
• Reactive liquid rubbers or other amino-functionalized polymers are preferred constituents of component (b). Examples are functionalized butadiene-nitrile rubbers (Hypro ATBN 1300 ⁇ 16).
• the curing agent (b) is present in liquid form.
• the proportion of the at least bifunctional curing agent (b) in the composition according to the present invention is 5 to 90 wt-%.
• the ratio of the reactive components in the compositions according to the present invention can be set by means of the equivalent ratio EEW/AHEW allowing the properties of the cured composition to be controlled. For example, excessive amine results in more flexible materials. An excess of epoxy groups can increase the strength of the cured composition in the subsequent heat treatment.
• an EEW/AHEW ratio of 0.8 to 1.2 is used, and particularly preferably the ratio is in a range of 0.95 to 1.05.
• Component (c) comprises compounds that can be cured by actinic radiation.
• component (c) comprises a radiation-curable hybrid compound (c1) having both one or more methacrylate groups and one or more epoxy groups.
• the hybrid compound (c1) is preferably bifunctional or of a higher functionality. Furthermore, with respect to the epoxy group crosslinkable by polyaddition, the hybrid compound (c1) is preferably at least bifunctional. However, hybrid compounds (c1) which are monofunctional with respect to the methacrylate groups, and bifunctional or of a higher functionality with respect to the epoxy groups, or vice versa, can be used as well.
• a radiation-curable hybrid compound (c1) carrying both one or more methacrylate groups and one or more epoxy groups can be obtained from the reaction of an isocyanatomethacrylate (c2) with a hydroxy-functional epoxy-containing compound (c3).
• catalysts can be used for acceleration of this reaction.
• Suitable isocyanatomethacrylates (c2) are, for example, reaction products such as can be obtained by reacting aliphatic, cycloaliphatic and/or aromatic at least bifunctional isocyanates (c4) with hydroxy-functional methacrylates (c5) according to a method from DE 3 025 227A1.
• the diisocyanate is used in a surplus of 20 wt-% or more.
• Surplus non-reacted monomeric diisocyanates (c4) can optionally be separated from the reaction blend by distillation, for example by vacuum distillation by means of a thin-layer evaporator or a thin-film evaporator. Such distillation methods are described in the plastics manual vol. 7, “Polyurethanes”, G. W. Becker (editor), Hanser-Verlag, Kunststoff, 3 rd edition 1993, page 425.
• Suitable diisocyanates (c4) comprise hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diisocyanatodicyclohexylmethane, methylene diphenyl isocyanate, toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, commercially available under the trade name Desmodur from Covestro AG, and meta-tetramethylxylylene diisocyanate from Allnex Germany GmbH.
• hydroxy-functional methacrylates are 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and glycerol dimethacrylate, commercially available under the trade name Visiomer from Evonik Performance Materials GmbH, as well as pentaerythritol trimethacrylate or mixtures of said raw materials.
• Suitable catalysts accelerating the reaction of isocyanate groups with hydroxy groups comprise organometallic compounds of tin, iron, titanium or bismuth such as dibutyltin or dioctyltin diacetate, dibutyltin or dioctyltin dilaurate and tributyltin acetate.
• Further catalysts are tin(II) salts and bismuth(III) salts of carboxylic acids such as tin(II)-acetate, tin(II)-2-ethylhexanoate and bismuth(III)-neodecanoate.
• said diisocyanates (c4) can also be reacted first with polyols, for example based on polyether, polycarbonate and/or polybutadiene, as long as an NCO/OH ratio of at least 2:1 is maintained. Eventually, the thus chain-extended bifunctional isocyanates can be reacted with hydroxy-functional methacrylates (c5).
• hydroxymethacrylates of a higher functionality can be useful for synthesizing the hybrid compound (c1).
• Methacrylate functionalities of at least 2 are preferred.
• Hydroxymethacrylates of a higher functionality (c5) are obtainable from the esterification of at least trifunctional alcohols with methacrylic acid.
• isocyanatomethacrylates (c2) can also be used for the reaction with hydroxy-functional epoxy-containing compounds (c3).
• Such isocyanatomethacrylates (c2) e.g. 2-isocyanatoethyl methacrylate or 2-(2-isocyanatoethyloxy)ethyl methacrylate, are available under the labels Karenz MOI or Karenz MOI-EG from Showa Denko Europe GmbH.
• hydroxy-functional epoxy-containing compounds (c3) are oligomeric or polymeric glycidyl ethers of bisphenols such as bisphenol A-based epoxy resins (e.g. DowDupont D.E.R. 671) or bisphenol F-based epoxy resins (e.g. Kukdo KD-9004).
• bisphenol A-based epoxy resins e.g. DowDupont D.E.R. 671
• bisphenol F-based epoxy resins e.g. Kukdo KD-9004
• Hydroxy-functional epoxy-containing compounds (c3) having a hydroxy functionality of 2 or more are preferably used.
• the hybrid compounds according to the present invention (c1) preferably contain more than one radiation-curable methacrylate group.
• compound (c1) also having, apart from at least one methacrylate group, at least one epoxy group, can be obtained by reaction of methacrylate-functionalized silanes (c6) with hydroxy-functional epoxides (c3) in a condensation reaction.
• the reaction occurs at an alkoxysilane/OH ratio of at least 2:1 in the presence of a suitable catalyst such as a Lewis acid on the basis of tin, titanium or zinc, in particular dibutyltin dilaurate, dioctyltin dilaurate or zinc(II)-acetylacetonate.
• amine catalysts such as aliphatic tertiary amines or unsaturated bicyclic amines, in particular triethylamine or diazabicycloundecene, can be used.
• the surplus of non-reacted methacrylalkoxysilane (c6) can be separated by distillation.
• compounds (c6) comprise 3-methacryloxypropyltrimethoxysilane, methacryloxymethyl)methyldimethoxysilane, methacryloxymethyltrimethoxysilane and 3-methacryloxypropyltriacetoxysilane, available from Wacker under the trade names GF 31, XL 32, XL 33 and GF 39.
• component (c1) inert solvents such as tetrahydrofuran, acetone or ethyl acetate, which can be removed by distillation after synthesis.
• Monofunctional epoxy compounds from the group of component (a) can be selected as reactive diluents.
• radiation-curable hybrid compounds with acrylate groups in component (c) is not preferred as they can react, after mixing of the components, by addition to the amine curing agent (b).
• the addition reaction of the amine curing agent to the double bond is substantially slower, the desired epoxy-amine polyaddition dominates, allowing the formation of a network that, after curing, has comparable mechanical properties in both the irradiated and non-irradiated zones.
• compositions according to the present invention can be tolerated as long as the desired processing time can be maintained and the mechanical properties of the cured composition in the irradiated and non-irradiated areas do not differ from each other to an extent undesired for the respective application.
• the proportion of the hybrid compound (c1) in the composition according to the present invention is preferably selected such that the amount of substance of radiation-curable methacrylate groups of the hybrid compounds is 50 to 100%, preferably 70 to 100%, each based on the radiation-curable equivalent weight (SEW) of the composition.
• an additional radiation-curable compound (c7) in the compositions according to the present invention in an amount of at most 50%, based on the radiation-curable equivalent weight (SEW) of the composition.
• the additional radiation-curable compound (c7) is preferably a (meth)acrylate-containing compound that is bifunctional or of a higher functionality, more preferably an at least bifunctional methacrylate.
• the (meth)acrylate-containing compound that is bifunctional or of a higher functionality (c7) is present in a proportion of at most 30%, based on the radiation-curable equivalent weight (SEW) of the composition. Proportions of more than 50% of the additional radiation-curable compound can massively change the mechanical properties of the cured composition in shadow zones as compared to irradiated areas and are thus not in the sense of the invention.
• a combination of several radiation-curable compounds (c7) is also in the sense of the invention as long as a proportion of 50%, based on the radiation-curable equivalent weight (SEW) of the composition, is not exceeded.
• SEW radiation-curable equivalent weight
• Examples of commercially available at least bifunctional methacrylates comprise 1,4-butanediol dimethacrylate (Sartomer SR214), bisphenol A glycidyl methacrylate (bisGMA, Esstech Inc.) diurethane dimethacrylate (VISIOMER HEMATMDI, Evonik Industries) or trimethylolpropane trimethacrylate (Sartomer SR350D).
• a suitable acrylate is, for example, trimethylolpropane triacrylate (Sigma Aldrich).
• component (c) is present in a proportion of at least 10 wt-%, preferably in a proportion of at least wt-% and particularly preferably of at least 30 wt-%.
• the maximum proportion of component (c) is up to 80 weight percent.
• the epoxy groups of the radiation-curable compounds (c) have to be considered when calculating the EEW.
• the bifunctional epoxy compound of component (a) is not necessary.
• the composition preferably contains both an at least bifunctional epoxy compound of component (a) and a hybrid compound (c1) with one or more epoxy groups in the molecule.
• the compositions also contain a photoinitiator (d) to activate radical polymerization.
• a photoinitiator to activate radical polymerization.
• radical photoinitiators the usual commercially available compounds can be used, such as ⁇ -hydroxyketones (Irgacure 184, Irgacure 2959), benzophenone, ⁇ , ⁇ ′-diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651), 4-isopropyl phenyl-2-hydroxy-2-propylketone, 1-hydroxycyclohexylphenylketone, isoamyl-p-dimethylaminobenzoate, methyl-4-dimethylaminobenzoate, methyl-o-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobuty
• the IRGACURETM types from BASF SE can be used as UV-photoinitiators, such as the IRGACURE 500, IRGACURE 1179, IRGACURE 745, IRGACURE 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), IRGACURE 907 (2-methyl-4′-(methylthio)-2-morpholinopropiophenone), IRGACURE 1300 ( ⁇ -aminoketone), IRGACURE 819DW, IRGACURE 2022, IRGACURE 2100, IRGACURE 250, IRGACURE TPO-L types.
• the DAROCURTM types from BASF SE can be used, such as the DAROCUR MBF, DAROCUR 1173 and DAROCUR 4265 types.
• the photoinitiator used as component (d) in the compositions according to the present invention can preferably be activated by actinic radiation of a wavelength from 200 to 600 nm, particularly preferably from 320 to 480 nm.
• the photoinitiator can be combined with a suitable sensitizing agent.
• Liquid photoinitiators such as Irgacure TPO-L are particularly preferred.
• the photoinitiator (d) is preferably present in a proportion of 0.01 to 5 wt-%, based on the total weight of the reactive components (a) to (e).
• compositions according to the present invention e.g. amines, alcohols and/or metal salts can be used as accelerators.
• tertiary amines such as tris-(dimethylaminomethyl)phenol available from Evonik under the trade name Ancamine K54 are suitable as amines.
• the corresponding alcohols acting as an accelerator especially comprise phenols such as p-tert-butylphenol (Songnox PTBP), cardanol (Cardolite NC-700) or nonylphenol and their derivatives, as well as benzyl alcohol.
• Metal salts such as Ca(NO 3 ) 2 or Ca(OTf) 2 as well as metal salt complexes can also be used to accelerate epoxy curing.
• the accelerator (e) is preferably present in a proportion of 0.01 to 5 wt-%, based on the total weight of the reactive components (a) to (e).
• the accelerator (e) is preferably incorporated in the curing agent component (B).
• compositions according to the present invention can contain further additives (f).
• Preferred additives (f) are toughness modifiers such as core-shell particles (Kaneka KaneAceTM series, Dow ParaloidTM EXL series, Wacker Genioperl®) or block copolymers, reactive elastifying agents (such as blocked isocyanate prepolymers according to U.S. Pat. No. 5,278,257 A), colorants, pigments, fluorescent agents, thixotropic agents, thickeners, stabilizers, antioxidants, plasticizers, fillers, flame retardants, corrosion inhibitors, inert diluents, catalysts, leveling and wetting additives and adhesion promoters, as well as combinations thereof.
• toughness modifiers such as core-shell particles (Kaneka KaneAceTM series, Dow ParaloidTM EXL series, Wacker Genioperl®) or block copolymers, reactive elastifying agents (such as blocked isocyanate prepolymers according to U.
• inorganic and organic fillers can be used as fillers. These can be contained in the composition according to the present invention in a proportion of 0 to 90 wt-%, based here on the total weight of the composition from components (a) to (f). All of the other said additives are preferably present in the compositions according to the present invention in a proportion of 0 to 20 wt-%, also based on the total weight of the composition.
• hindered phenols e.g. 2,6-di-t-butyl-4-methylphenol
• substituted hydroquinone monoalkyl ethers MeHQ; hydroxyquinone monomethyl ether
• hindered amine light stabilizers HALS
• phosphites or aromatic thioethers
• said stabilizers are already used in the production of the hybrid compound (c1).
• the composition according to the present invention is preferably provided as a two-part composition having a resin component (A) and a curing agent component (B) physically separated from the resin component (A).
• the resin component (A) preferably comprises the at least bifunctional epoxy compound of component (a), the hybrid compound (c1) and the photoinitiator (d).
• the curing agent component (B) preferably comprises the nitrogen-based curing agent of component (b) and the accelerator (e).
• composition according to the present invention consists of the following components:
• composition according to the present invention consists of the following components, each based on the total weight of components a) to e):
• An exemplary formulation of the two-part composition according to the present invention preferably comprises the following components, wherein the weight percentages mentioned are based respectively on the total weight of resin component (A) and curing agent component (B):
• the mixing ratio of resin component (A) to curing agent component (B) results from the equivalent weights EEW (epoxy equivalent weight) [g/mol of epoxide] of resin component (A) and AHEW (active hydrogen equivalent weight) [g/mol of act-H] of curing agent component (B).
• EEW epoxy equivalent weight
• AHEW active hydrogen equivalent weight
• the mixing ratio of component (A) to component (B) is selected such that an EEW/AHEW equivalent weight ratio of 0.8 to 1.2, and particularly preferably of 0.95 to 1.05, is achieved.
• the formulations consist of said components.
• compositions according to the present invention are suitable for fast energy-efficient industrial processes with short cycle times which, at the same time, require the thermal load on the parts involved to be as low as possible.
• compositions according to the present invention are used as an adhesive, casting composition, molding composition or sealant for the bonding, casting, sealing or coating of substrates.
• the fields of application set out below are exemplary rather than final.
• compositions can be used for fast fixation of holders as used, for example, in aircraft interiors for the assembly of cables or attachment parts.
• the compositions according to the present invention are also useful for casting applications in which the geometry can be fixed by irradiation and thus the number of assembly devices can be reduced. They can also be used in the bonding of magnets during the manufacture of electric motors. Due to the large mass and heat capacity of the parts, curing at room temperature is particularly useful in this sector to save energy.
• compositions according to the present invention are suitable for the precision fabrication of parts, in particular optoelectronic elements.
• compositions according to the present invention can preferably be transferred into a dimensionally stable state by irradiation with actinic radiation of a wavelength ranging from 200 to 600 nm, preferably from 320 to 480 nm.
• actinic radiation of a wavelength ranging from 200 to 600 nm, preferably from 320 to 480 nm.
• the use of energy-saving LED lamps emitting light of a wavelength ranging from 365 nm to 405 nm is particularly preferred.
• the methacrylate groups of the hybrid compound (c1) and optionally of the additional radiation-curable compound (c7) are crosslinked by radical polymerization.
• the compositions fixed this way are sufficiently dimensionally stable, and can be quickly advanced to processing in further process steps before curing is completed.
• the penetration depth of the actinic radiation, and thus the thickness of the light-fixed layer, can be controlled by means of the irradiation dose, the amount and type of fillers and additives used, and the wavelength used.
• compositions according to the present invention achieve a sufficient green strength that is sufficient for further processing of the fabricated parts without additional irradiation in less than 10 h, preferably in less than 6 h, particularly preferably in less than 4 h.
• Final curing occurs at room temperature within 7 days, preferably within 5, and particularly preferably within 3 days.
• the curing reaction can be accelerated by heat.
• the compositions can be completely cured within 4 h, preferably within 2 h.
• curing can be completed typically within 2 h, preferably within 1 h.
• Temperature-graduated curing profiles are also in the sense of the invention.
• Heat input can occur, for example, in convection ovens, by thermodes, IR radiators, laser or induction.
• compositions according to the present invention offer the advantage in joining processes that parts or molded bodies can be fixed in their position by irradiation with actinic radiation.
• a corresponding method for the bonding, casting, molding or coating of substrates using the compositions according to the present invention preferably comprises the following steps:
• the first and second substrates, after joining, can optionally be aligned relative to each other before the composition is fixed by irradiation.
• Such an alignment is preferably required in the fabrication of optoelectronic parts such as camera modules (active alignment).
• compositions according to the present invention are irradiated at a wavelength of 365 nm with an intensity of 200 ⁇ 20 mW/cm 2 for a period of 60 s using a DELOLUX 20/365 LED lamp from DELO Industrie Klebstoffe GmbH & Co. KG.
• the processing time was determined according to DIN EN 14022:2010 (Method 1) using a Physica MCR302 rheometer from Anton Paar having a standardized PP20 measuring stamp with a measuring gap of 1000 ⁇ m and a temperature of +23° C.
• the processing time is defined as the period of time, starting from mixing of the components, within which the apparent viscosity
• the adhesive (3 g in total) was mixed manually by means of a spatula on a PE-coated mixing pad.
• the compositions according to the present invention are considered as unrestrictedly processable until their viscosity has doubled.
• the compositions according to the present invention can be unrestrictedly dosed within the processing time and fixed by irradiation.
• Crosslinking or “curing” is defined as a polymerization or addition reaction beyond the gel point.
• the gel point is the point at which the storage modulus G′ becomes equal to the loss modulus G′′. Curing of the specimens occurs at room temperature for 7 days.
• Room temperature is defined as 23 ⁇ 2° C.
• compositions are subjected to an optical assessment.
• a haptic test is performed using a plastic spatula.
• a non-absorbent coated cardboard with a thickness of 1.5 mm and an edge length of 100 mm ⁇ 174 mm is used.
• a start line parallel to the short edges (distance: approx. 15 to 30 mm) is marked on the specimen. Above the line, drops of the compositions to be tested of approx. 0.1 g are applied while the cardboard is laid on a horizontal surface. The specimen is kept in this position for 1 min. Then the drop of adhesive is optionally irradiated according to the parameters set out under the point “Irradiation”. Then, the specimen is placed vertically and remains in this position during the test period (24 h), wherein the adhesive, depending on its flowability, travels down a more or less longer distance. The test was performed at room temperature.
• the specimen is returned to the horizontal position and the run-off path of the adhesive is determined by measuring the distance traveled from the start line to the lowest end of the respective flow front. If the composition flows to the end of the specimen, the flow path to the end of the cardboard is measured and marked with a “greater-than” sign (“>x mm”).
• Tensile properties including modulus of elasticity, tensile strength and elongation at break were determined on the basis of DIN EN ISO 527-2:2012-06, using type 5A specimens.
• the test speed to determine the modulus of elasticity was 1 mm/min
• the test speed to determine the tensile strength and elongation at break was 10 mm/min.
• the test was performed at room temperature on an AllroundLine 20 kN universal test machine from Zwick Roell.
• the curing time was 7 days at room temperature in the dark.
• irradiation with actinic radiation for 60 s on both sides was performed directly after introducing the mixed composition into the curing mold.
• the glass transition temperature was determined by means of differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1:2017-2, using Al crucibles with a volume of 40 ⁇ l and a perforated lid in which the products were optionally irradiated according to the parameters set out under the point “Irradiation” and cured for 7 days at room temperature. Measurement was performed with a DSC2 from Mettler Toledo in two heating courses from 0° C. to 220° C., with a heat rate of 10 K/min in the first heating course and 20 K/min in the second heating course. To evaluate the T G , the half-step-height method according to ISO 11357-2:2013 was used in the second heating course.
• IPDI isophorone diisocyanate
• c4-1 333.44 g (1.50 mol) of isophorone diisocyanate (IPDI) (c4-1) was placed in a reaction vessel equipped with a suitable stirrer. 1.05 g of hydroquinone monomethyl ether (f2) and 1.05 g of 2,6-di-tert-butyl-4-methylphenol (f3) were added and dissolved under dry pressurized air. Then 0.50 g of dibutyltin dilaurate (f4) was added and the temperature was reduced to 15° C. At this temperature, 191.38 g (1.47 mol) of 2-hydroxyethyl methacrylate (c5-1) was added under constant stirring. Then the temperature was slowly increased to 50° C. The reaction was stirred for 3 hours at this temperature until an NCO content of 11.60% was achieved. A virtually colorless clear isocyanatomethacrylate (c2-2) was obtained.
• IPDI isophorone di
• the resin component (A) and the curing agent component (B) are weighed into a suitable PP box according to the mass fractions mentioned and mixed in the speed mixer. This occurs under ambient light that is outside the excitation wavelengths of the photoinitiator (d1) or any sensitizer.
• the examples according to the present invention from Table 1 contain, as the radiation-curable component (c), the hybrid compound (c1) which carries both epoxy groups and methacrylate groups.
• the methacrylate groups of the hybrid compound are present in the examples according to the present invention in a proportion of at least 50%, based on the radiation-curable equivalent weight (SEW) of the composition.
• Examples 1 to 10 according to the present invention are characterized in that they can be fixed by irradiation. After irradiation, the compositions are haptically solid and show no softening in the run-off test.
• the non-inventive Comparative Example 12 based on an acrylate-containing radiation-curable hybrid compound (c8) remains liquid after irradiation and softens in the run-off test.
• the processing time of Comparative Example 12 is reduced by more than half when directly compared to a formulation that is otherwise analogous but based on compound (c1-1) (Example 1 according to the present invention).
• Example 10 Apart from the hybrid compound (c1), Example 10 according to the present invention additionally contains tri methylolpropane triacrylate (c7-2) as an additional radiation-curable compound.
• the additional radiation-curable compound (c7-2) is present in a proportion of less than 50%, based on the radiation-curable equivalent weight of the composition. Still, the composition shows no significant disadvantages with regard to the mechanical properties in the irradiated and non-irradiated areas and the processing time. As compared to Example 3 according to the present invention, in which the analogous methacrylate (c7-1) is used as the additional radiation-curable compound, the processing time is reduced by only 5 minutes.
• Comparative Example 14 contains a curing agent showing a slow addition reaction to the acrylate groups of the hybrid compound (c8).
• Comparative Example 14 can be fixed by irradiation, the processing time is already reduced by more than 2 ⁇ 3 as compared to Example 4 according to the present invention based on the methacrylate-containing hybrid compound (c1-1).
• Examples 4 and 5 according to the present invention contain a curing agent (b1) based on a polyamidoimidazole.
• Example 5 additionally contains trimethylolpropane trimethylacrlyate (c7-1) as the additional radiation-curable compound.
• Comparative Example 13 contains only trimethylolpropane trimethylacrlyate (c7-1) but not the hybrid compound (c1) as the additional radiation-curable compound. This leads to significant differences in the mechanical properties of the cured composition in the irradiated and non-irradiated areas. For example, elongation at break differs by almost 20%, and the modulus of elasticity by factor 2.6. The glass transition temperature is 19° C. lower in the non-irradiated composition.
• Examples 1 to 3 according to the present invention contain, as the curing agent, a polyether diamine (b2).
• Example 1 according to the present invention contains, as the radiation-curable compound (c), only the hybrid compound (c1-1).
• Examples 2 and 3 according to the present invention additionally contain TMPTA (c7-1) up to a proportion of 49%, based on the total proportion of the radiation-curable groups (SEW) of component (c). Up to this concentration, the mechanical properties of the cured masses differ only slightly between the irradiated and non-irradiated zones.
• composition of Comparative Example 11 only 7% of the radiation-curable methacrylate groups result from the hybrid compound (c1-1), based on the SEW of the composition.
• the composition can be light-fixed without restrictions, it shows, after curing, a relative difference of more than 50% in the mechanical properties, in particular with regard to elongation at break, between the irradiated and non-irradiated composition.
• Examples 6, 7, 9 according to the present invention contain curing agent mixtures on the basis of polyether amines, cycloaliphatic amines and aromatic benzyl amines.
• a curing agent (b6) obtained by partial reaction of a bisphenol A epoxy resin (Epikote Resin 828LVEL, (a4)) and MXDA (b4) (manufacturing example 5) was used.
• Example 8 contains, as the curing agent, a commercially available mixture of MXDA (b4) and phenalkamines (b5).
• the masses according to the present invention are characterized by a broad formulation range with regard to the curing agent without the mechanical properties of the cured masses such as glass transition temperature, modulus of elasticity and elongation at break significantly differing between the irradiated and non-irradiated areas of the composition.
• the examples according to the present invention have variable processing times without the described properties being negatively affected.

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